CHEM 2323

Organic Chemistry 1

Dr. Sumudu Wijenayake

Office BE 3.330C

1
2013 Pearson Education, Inc.
 Ochem
Preparation Read class notes before the lecture

Lecture, Text Book, Model kits,

Understanding
Online resources
Concepts
How to study for Ochem ?

Group discussions, Practice problems

Practice
in the book, Previous exams
Get help early:
SI, PLTL, Professor and TA
Office hours
Review
2
2013 Pearson Education, Inc.
 Outline
1. What is organic chemistry ?
2. Principles of atomic structure
3. Bond formation
4. Electronegativity and bond polarity
5. Lewis structures and formal charges
6. Resonance
7. Structural formulas
8. Acids and bases and their relative strengths

Chapter 1 3
2013 Pearson Education, Inc.
 Organic Chemistry
Organic chemistry is the chemistry of carbon compounds.
Non carbon atoms like H, N, S, O also involve in forming carbon
compounds

Materials chemistry
Medicinal use Protein chemistry
Biochemistry
Anti caser drug
Alkaloid a natural product

Codeine Taxol Life

Separation- membranes

Organic electronics

2013 Pearson Education, Inc. Chapter 1 4

 Review Gen Chem

Why ? To understand Structure property relationships in Organic

chemistry

Organic Physical properties: Polarity, Solubility,

Molecule melting points..
Structure Stereochemistry
Specific applications
Reactivity leads to a variety of compounds

How you explain:

Need to understand electron configuration,

bonding, functional groups, electronegativity, acid base nature..ect

5
2013 Pearson Education, Inc.
Gen Chem
 Electronic Structure of the Atom

An atom has a dense, positively

charged nucleus surrounded by
a cloud of electrons.

The electron density is highest

at the nucleus and drops off
exponentially with increasing
distance from the nucleus in any
direction.

2013 Pearson Education, Inc. Chapter 1 6

 The 2p Orbitals

There are three 2p orbitals,

oriented at right angles to
each other.

Each p orbital consists of

two lobes.

Each is labeled according to

its orientation along the x, y,
or z axis.

2013 Pearson Education, Inc. Chapter 1 7

 Electronic Configurations of Atoms

Valence electrons are electrons on the outermost shell

of the atom.
2013 Pearson Education, Inc. Chapter 1 8
 Electronic Configurations

The aufbau principle states to

fill the lowest energy orbitals first.
Ex: Be

Hunds rule states that when

there are two or more orbitals of
the same energy (degenerate),
electrons will go into different
orbitals rather than pairing up in
the same orbital.
Ex: C, N

2013 Pearson Education, Inc. Chapter 1 9

 Ionic Bonding
To obtain a noble gas configuration (a full valence
shell), atoms may transfer electrons from one atom to
another.
The atoms, now bearing opposite charges, attract each
other, forming an ionic bond.

Ionic bonds can be present in organic molecules

2013 Pearson Education, Inc. Chapter 1 10

 Covalent Bonding
Electrons are shared between the atoms to complete the octet.

When the electrons are shared evenly, the bond is said to be

nonpolar covalent, or pure covalent.

When electrons are not shared evenly between the atoms, the
resulting bond will be polar covalent.

Most common type

of bonding in ochem is
Covalent bonding

Why ?
2013 Pearson Education, Inc. Chapter 1 11
 Pauling Electronegativities
Electronegativity: is a measure of the tendency of an atom to attract a bonding pair of
electrons
Higher the tendency higher the electronegativity

What are the periodic trends of EN

and why ?

Importance:
Electronegativities can be used to predict whether a bond will be polar and the
direction of its dipole moment.
Since the electronegativities of carbon and hydrogen are similar, CH bonds are
considered to be nonpolar.
2013 Pearson Education, Inc. Chapter 1 12
 Dipole Moment

Dipole moment is defined to be the amount of charge separation (d)

multiplied by the bond length (m).

Charge separation is shown by an electrostatic potential map

(EPM), where red indicates a partially negative region and blue
indicates a partially positive region.

2013 Pearson Education, Inc. Chapter 1 13

 Lewis Structures
Use a dash or a pair of dots to denote bond
Also do not forget to show non bonded electrons/lone pairs

CH4 NH3
H Nitrogen: 5 e
Carbon: 4 e 3 H@1 e ea: 3 e H N H
4 H@1 e ea: 4 e
8e
H C H 8e
H
H

H2O Cl2
Oxygen: 6 e
2 H@1 e ea: 2 e H O H 2 Cl @7 e ea: 14 e Cl Cl
8e
Exam
2013 Pearson Education, Inc. Chapter 1 14
 Bonding Patterns
Important to know:

Valence # Bonds # Lone Pair

electrons Electrons
C
4 4 0

N
5 3 1

O
6 2 2
Halides
(F, Cl, Br, I) 7 1 3
Number of bonds an atom forms is called its valence
2013 Pearson Education, Inc. Chapter 1 15
 Nonbonding Electrons

Also called lone pairs.

Nonbonding electrons are valence shell electrons that are not
shared between atoms.

When you draw lewis structures you need to show lone pairs
2013 Pearson Education, Inc. Chapter 1 16
 Multiple Bonding

Sharing two pairs of electrons is called a double bond.

Sharing three pairs of electrons is called a triple bond.
Important in alkenes, alkynes

2013 Pearson Education, Inc. Chapter 1 17

 Formal Charges
Formal charge of a given atom = [group number ] [nonbonding electrons ]
[shared electrons]
H3O+ NO++
N O O:6 2 (6) = +1
H +O H
N:5 2 (6) = 0
H
O: 6 2 (6) = +1

How about O in water and in OH- ?

FC help us to predict how a molecule behaves (+ FC attract electrons, - FC

donate electrons)

Formal charges are a way of keeping track of electrons.

They may or may not correspond to actual charges in the molecule.

2013 Pearson Education, Inc. Chapter 1 18

 Solved Problem 1
Compute the formal charge (FC) on each atom in H3N BH3.

1. Remember the Definition:

Formal charge = [group number ] [nonbonding electrons ] [shared electrons]
2. Draw the lewis structure

2013 Pearson Education, Inc. Chapter 1 19

 Work enough problems to
become familiar with these
bonding patterns so you can
recognize other patterns as
being either unusual or wrong.

Questions : Problem 1.6 (Page 13)

Study problems:1-22,1-23,1-24,1-35,1-25,1-26

2013 Pearson Education, Inc. Chapter 1 20

 Resonance Forms

Exam
Chapter 1 21
2013 Pearson Education, Inc.
 Resonance Forms
The structures of some compounds are not adequately represented by
a single Lewis structure.

Resonance forms are Lewis structures that can be interconverted by

moving electrons only.

The true structure will be a hybrid between the contributing resonance

forms. In the actual molecule the charge is delocalized.
Resonance stabilized/anion or a cation
Exam
They are not in equilibrium

2013 Pearson Education, Inc. Chapter 1 22

 Resonance Forms
Resonance forms may/may not have the same energy

Resonance forms can be compared using the following

criteria, beginning with the most important:
Most stable resonance form
1. Has as many octets as possible.
2. Has as many bonds as possible.
3. Has the negative charge on the most electronegative
atom.
4. Has as little charge separation as possible.

Depending on these factors resonance forms could or

could not contribute equally for the actual structure Exam
2013 Pearson Education, Inc. Chapter 1 23
 Major and Minor Contributors
The major contributor is the one in which all the atoms
have a complete octet of electrons. (Most important factor)

2013 Pearson Education, Inc. Chapter 1 24

 Major and Minor Contributors (Continued)
When both resonance forms obey the octet rule,
the major contributor is the one with the negative charge on
the most electronegative atom.

N C O N C O

The oxygen is more electronegative,

so it should have the negative
charge.

Which is the major one ?

2013 Pearson Education, Inc. Chapter 1 25

 Non-Equivalent Resonance

Opposite charges should be on adjacent atoms.

CH3 O N O CH3 O N O
MAJOR MINOR

The most stable one is the one with the smallest

separation of oppositely charged atoms.

2013 Pearson Education, Inc. Chapter 1 26

 Solved Problem 2

Draw the important resonance forms for [CH3OCH2]+. Indicate which structure is the major and minor
contributor or whether they would have the same energy.

Solution

The first (minor) structure has a carbon atom with only six electrons around it. The second (major)
structure has octets on all atoms and an additional bond.

2013 Pearson Education, Inc. Chapter 1 27

 Solved Problem 3

Draw the resonance structures of the compound below. Indicate which structure is the major and minor
contributor or whether they would have the same energy.

Solution

Both of these structures have octets on oxygen and both carbon atoms, and they have the same number
of bonds. The first structure has the negative charge on carbon, the second on oxygen. Oxygen is the
more electronegative element, so the second structure is the major contributor.

2013 Pearson Education, Inc. Chapter 1 28

 Organic Chemistry Language

Chapter 1 29
2013 Pearson Education, Inc.
 Condensed Structural Formulas
Organic Chemistry Language
Lewis (What we know) Condensed
H H Atoms bonded to
1 2 Central atoms
CH3CH3
H C C H
H H Central atoms

Condensed forms are written without showing all the individual

bonds.

Atoms bonded to the central atom are listed after the central atom
(CH3CH3, not H3CCH3).

2013 Pearson Education, Inc. Chapter 1 30

 Condensed Structural Formulas

Common name Condensed

Lewis structure structural formula
If there are two or more identical groups, parentheses and a subscript
may be used to represent them.
2013 Pearson Education, Inc. Chapter 1 31
 Condensed Structural Formulas

2013 Pearson Education, Inc. Chapter 1 32

 Line-Angle Drawings
Organic Chemistry Language

H H H H
1 2 3 4 C C
H C C C C H C C
H H H H
Sometimes called skeletal structure or stick figure.

Bonds are represented by lines, and carbons are present

where a line begins or ends and where two lines meet.

Hydrogens attached to carbon are not shown. In the

condensed structures Hs were indicated
Nitrogen, oxygen, and halides must be shown.

2013 Pearson Education, Inc. Chapter 1 33

 Line-Angle Drawings

H H H H H O 1 2 3 4 5 6
1 2 3 4 5 6 O
H C C C C C C
H H
H H H H H

Atoms other than carbon must be shown.

Double and triple bonds must also be shown.

2013 Pearson Education, Inc. Chapter 1 34

 Condensed structural and Line-Angle Formulas

Normal Condensed Line

structural Angle
2013 Pearson Education, Inc. Chapter 1 35
 Acids, Bases, Nucleophiles,
Electrophiles and their relative
strengths

Exam : Ranking Questions

Chapter 1 36
2013 Pearson Education, Inc.
 Arrhenius Acids and Bases
Arrhenius acids dissociate in water to give H3O+ ions.

Stronger acids dissociate to a greater degree than weaker

acids.

Arrhenius bases are substances that dissociate in water to

give hydroxide ions.

Stronger bases (NaOH) dissociate more than weaker bases (Mg(OH)2).

2013 Pearson Education, Inc. Chapter 1 37

 Brnsted-Lowry Acids and Bases
Brnsted-Lowry acids are any species that donate a proton.
Brnsted-Lowry bases are any species that can accept a proton.

2013 Pearson Education, Inc. Chapter 1 38

 Conjugate Acids and Bases

Conjugate acid: when a base accepts a proton, it becomes an acid

capable of returning that proton.
Conjugate base: when an acid donates its proton, it becomes capable
of accepting that proton back.

2013 Pearson Education, Inc. Chapter 1 39

 Acid /base strength EXAM

Can be expressed using Ka values

How?
Higher the Ka stronger the acid; pka ?

Acid strength is inversely related to the strength of the conjugate

base
HCl + H2O..
CH3-OH + H2O

The stronger the acid, weaker the conjugate base

The weaker the acid, stronger the conjugate base
Acid base reactions favor the weaker acid weaker base direction

Chapter 1 40
2013 Pearson Education, Inc.
 Ka pKa

Chapter 1 41
2013 Pearson Education, Inc.
Structure property What are the factors affecting
relationships Acid strength

Condition: The conjugate base should be stable in its

anionic form
1. Electronegativity of the conjugate base

2. Size of the conjugate base

3. Resonance stabilization of the conjugate base

4. Inductive effects (Presence of electron withdrawing groups

stabilize the conjugate base through bonds)

Chapter 1 42
2013 Pearson Education, Inc.
1.Effect of Electronegativity on pKa (acidity)

As the bond to H becomes more polarized, H becomes

more positive and the bond is easier to break.

2013 Pearson Education, Inc. Chapter 1 43

 2. Effect of Size on pKa (Acidity)

As size increases, the H is more loosely held and the bond is easier to
break.
A larger size also stabilizes the anion.

2013 Pearson Education, Inc. Chapter 1 44

 3. Effect of Resonance on pKa(Acidity)

If the negative charge on an atom can be delocalized over two or more atoms,
the acidity of that compound will be greater than when the negative charge cannot
be delocalized.

The ethoxide anion is less acidic than the acetate ion simply because the acetate
ion can delocalize the negative charge.

Methanesulfonic acid can delocalize the charge in three different resonance forms,
making it more acidic than the acetate ion.
2013 Pearson Education, Inc. Chapter 1 45
 4.Inductive effects (Through Bonds)
Presence of electron withdrawing groups stabilizes the conjugate base

Chapter 1 46
2013 Pearson Education, Inc.
 Lewis Acids and Lewis Bases

Lewis bases are species with available electrons than can

be donated to form a new bond.

Lewis acids are species that can accept these electrons to

form new bonds.

Since a Lewis acid accepts a pair of electrons, it is called

an electrophile (electron loving).

2013 Pearson Education, Inc. Chapter 1 47

 Nucleophiles and Electrophiles

Nucleophile: Donates electrons to a nucleus with

an empty orbital.

Electrophile: Accepts a pair of electrons.

When forming a bond, the nucleophile attacks the

electrophile, so the arrow goes from negative to
positive. (in other words electrons move)

When breaking a bond, the more electronegative

atom receives the electrons.
2013 Pearson Education, Inc. Chapter 1 48
 Nucleophiles and Electrophiles

2013 Pearson Education, Inc. Chapter 1 49

 Condensed Structural Formulas

Lewis Condensed

H H Br H Br
1 2 3 4
H C C C C H CH3CH2CHCH3
H H H H

H H O H O
1 2 3 4
H C C C C H HOCH2CH2CCH3
OH H H
2013 Pearson Education, Inc. Chapter 1 50
 Condensed Structural Formulas

2013 Pearson Education, Inc. Chapter 1 51

 Calculating Empirical Formulas

The following are items that need to be

considered when calculating empirical
formulas:
Given % composition for each element,
assume 100 g.
Convert the grams of each element to moles.
Divide by the smallest number of moles to get
ratio.
Molecular formula may be a multiple of the
empirical formula.
2013 Pearson Education, Inc. Chapter 1 52
 If an elemental analysis does
not add up to 100%, the
missing percentage is assumed
to be oxygen.

2013 Pearson Education, Inc. Chapter 1 53

Structure property Resonance Forms for the
relationships
Acetate Ion

When acetic acid loses a proton, the resulting acetate ion has a
negative charge delocalized over both oxygen atoms.

Each oxygen atom bears half of the negative charge, and this
delocalization stabilizes the ion.

Each of the carbonoxygen bonds is halfway between a single bond

and a double bond and is said to have a bond order of 1.

Acetic acid shows moderate acidity (pka 4.7)

2013 Pearson Education, Inc. Chapter 1 54